US10287229B2 - Method of continuously recovering (meth)acrylic acid - Google Patents

Method of continuously recovering (meth)acrylic acid Download PDF

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US10287229B2
US10287229B2 US15/752,841 US201615752841A US10287229B2 US 10287229 B2 US10287229 B2 US 10287229B2 US 201615752841 A US201615752841 A US 201615752841A US 10287229 B2 US10287229 B2 US 10287229B2
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meth
acrylic acid
reboiler
waste liquid
natural circulation
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US20180244601A1 (en
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Yoon Jae MIN
Se Won BAEK
Jong Hun SONG
Sul Hee YOO
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LG Chem Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
    • C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/14—Fractional distillation or use of a fractionation or rectification column
    • B01D3/32—Other features of fractionating columns ; Constructional details of fractionating columns not provided for in groups B01D3/16 - B01D3/30
    • B01D3/322—Reboiler specifications
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
    • C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
    • C07C57/03—Monocarboxylic acids
    • C07C57/04—Acrylic acid; Methacrylic acid

Definitions

  • the present disclosure relates to a method of continuously recovering (meth)acrylic acid, and more particularly, to a method of continuously recovering (meth)acrylic acid from a (meth)acrylic acid waste liquid including (meth)acrylic acid, (meth)acrylic acid dimers, and high-boiling-point by-products.
  • Methodacrylic acid which is a main raw material of a superabsorbent polymer (SAP) is generally obtained by gas-phase oxidation reaction of propylene, etc.
  • a raw material compound such as propane, propylene, (meth)acrolein, etc.
  • a catalyst to obtain a (meth)acrylic acid-containing mixed gas, which is then condensed or absorbed into an absorption solvent and collected as a (meth)acrylic acid-containing solution.
  • low-boiling-point components such as the absorption solvent, (meth)acrylic acid dimers, (meth)acrylic acid oligomers, and high-boiling-point by-products such as maleic acid are separated by a series of purification processes to obtain crude (meth)acrylic acid.
  • a waste liquid obtained as a waste material in the process of separating the high-boiling-point by-products includes part of unrecovered (meth)acrylic acid, (meth)acrylic acid dimers, and high-boiling-point by-products such as maleic acid which are generated during the purification process.
  • (meth)acrylic acid waste liquid a large amount of the (meth)acrylic acid dimers included in the waste liquid (hereinafter referred to as ‘(meth)acrylic acid waste liquid’) may be recovered as (meth)acrylic acid through a high-temperature or catalytic reaction.
  • Patent Document 1 U.S. Pat. No. 6,252,110 B1 (2001 Jun. 26)
  • the present disclosure provides a method of continuously recovering (meth)acrylic acid which enables stable operation of a continuous process while simplifying equipment configuration of a destructive distillation process of recovering (meth) acrylic acid from a (meth) acrylic acid waste liquid.
  • a method of continuously recovering (meth)acrylic acid from a (meth)acrylic acid waste liquid including (meth)acrylic acid, (meth)acrylic acid dimers, and high-boiling-point by-products is provided,
  • a destructive distillation system 500 including a distillation column including a (meth)acrylic acid waste liquid-receiving section 510 and a distillation section 520 at the top portion thereof, and a natural circulation type of reboiler 550 which is connected to the distillation column and heats a liquid discharged from the lower portion of the distillation column by passing the liquid through a plurality of heat exchanger tubes to supply the liquid to the (meth)acrylic acid waste liquid-receiving section 510 of the distillation column, and
  • the destructive distillation system 500 is operated such that the maximum height of the (meth)acrylic acid waste liquid in the (meth)acrylic acid waste liquid-receiving section 510 corresponds to 85% or more of the height of the top end of the heat exchanger tube of the natural circulation type of reboiler 550 .
  • (meth)acrylic acid means acrylic acid and/or methacrylic acid.
  • the term ‘(meth)acrylic acid-containing mixed gas’ refers to a mixed gas which may be produced during synthesis of (meth)acrylic acid by gas-phase oxidation reaction.
  • the (meth)acrylic acid-containing mixed gas may be obtained by gas-phase oxidation of one or more compounds (‘raw material compounds’) selected from the group consisting of propane, propylene, butane, isobutylene, and (meth)acrolein in the presence of a catalyst.
  • the (meth)acrylic acid-containing mixed gas may include (meth)acrylic acid, non-reacted raw material compounds, (meth)acrolein, an inert gas, carbon monoxide, carbon dioxide, water vapor, and various organic by-products (acetic acid, low-boiling-point by-products (light ends), high-boiling-point by-products (heavies), etc.).
  • the ‘low-boiling-point by-products’ (light ends) or ‘high-boiling-point by-products’ (heavies) are kinds of by-products that may be generated in the process of preparing and recovering desired (meth)acrylic acid, and generally refer to compounds having a smaller or larger molecular weight than (meth)acrylic acid.
  • natural circulation may be caused by a density difference due to a temperature gradient between a material (a liquid to be distilled) injected into the reboiler and a material (a liquid-gas mixture produced by heat exchange) discharged from the reboiler.
  • the natural circulation type of reboiler When this natural circulation type of reboiler is stably operated, an operating part such as a pump is not required, and thus there are advantages that equipment configuration may be simplified and energy consumption may be reduced.
  • the natural circulation type of reboiler is used for a liquid having viscosity of 0.5 cP or less under operating conditions and a low fouling tendency at the inner wall of the heat exchanger tube of the reboiler in the case where a pressure in the reaction system is high.
  • the (meth)acrylic acid waste liquid obtained during the process of preparing (meth)acrylic acid has high viscosity of 20 cP to 60 cP at 100° C. to 150° C., and shows a high fouling tendency at the inner wall of the heat exchanger tube of the reboiler when it is exposed to a high temperature.
  • a destructive distillation system 500 including a distillation column including a (meth)acrylic acid waste liquid-receiving section 510 and a distillation section 520 at the top portion thereof, and a natural circulation type of reboiler 550 which is connected to the distillation column and heats the liquid discharged from the bottom of the distillation column by passing the liquid through a plurality of heat exchanger tubes to supply the liquid to the (meth)acrylic acid waste liquid-receiving section 510 of the distillation column, and
  • the destructive distillation system 500 is operated such that the maximum height of the (meth)acrylic acid waste liquid in the (meth)acrylic acid waste liquid-receiving section 510 corresponds to 85% or more of the height of the top end of the heat exchanger tube of the natural circulation type of reboiler 550 .
  • the present disclosure relates to the method of continuously recovering (meth)acrylic acid from a (meth)acrylic acid waste liquid including (meth)acrylic acid, (meth)acrylic acid dimers, and high-boiling-point by-products by destructive distillation.
  • FIG. 1 shows an apparatus for preparing (meth)acrylic acid and a process diagram showing an overall flowchart.
  • the (meth)acrylic acid waste liquid is a liquid discharged from the lower part of a high-boiling-point by-product separation column 400 .
  • the (meth)acrylic acid waste liquid is obtained as waste in the process of separating the high-boiling-point by-products during a series of purification processes of the (meth)acrylic acid-containing solution, and includes part of unrecovered (meth)acrylic acid, and (meth)acrylic acid dimers and high-boiling-point by-products such as maleic acid which are generated during the purification process.
  • the (meth)acrylic acid-containing solution refers to a solution collected by condensing a (meth)acrylic acid-containing mixed gas or absorbing the (meth)acrylic acid-containing mixed gas into an absorption solvent, in which the (meth)acrylic acid-containing mixed gas is obtained by subjecting a raw material compound such as propane, propylene, (meth)acrolein, etc. to gas-phase oxidation reaction in the presence of a catalyst.
  • a raw material compound such as propane, propylene, (meth)acrolein, etc.
  • the (meth)acrylic acid waste liquid includes a large amount of (meth)acrylic acid dimers which are formed during the purification process, and the (meth)acrylic acid dimers may be recovered as (meth)acrylic acid by decomposition through a high-temperature or catalytic reaction.
  • FIGS. 2 and 3 show a destructive distillation system which is used for continuous recovery of (meth)acrylic acid from the (meth)acrylic acid waste liquid and a process diagram showing a flowchart according to embodiments of the present disclosure, respectively.
  • the recovery of (meth)acrylic acid may be performed in the destructive distillation system 500 including a distillation column including a (meth)acrylic acid waste liquid-receiving section 510 and a distillation section 520 at the top portion thereof, and a natural circulation type of reboiler 550 which is connected to the distillation column and heats the liquid discharged from the lower portion of the distillation column by passing the liquid through a plurality of heat exchanger tubes to supply the liquid to the (meth)acrylic acid waste liquid-receiving section 510 of the distillation column.
  • the (meth)acrylic acid waste liquid as a feed is supplied to the distillation column and received in the (meth)acrylic acid waste liquid-receiving section 510 at an arbitrary liquid level.
  • the (meth)acrylic acid waste liquid-receiving section 510 is maintained at a temperature level at which the thermal decomposition of the (meth)acrylic acid waste liquid may occur.
  • the destructive distillation system 500 may be operated such that the temperature of the (meth)acrylic acid waste liquid-receiving section 510 is maintained at 100° C. to 200° C., and preferably 130° C. to 180° C.
  • This temperature control may be performed by supplying a heating medium, which is heated to a predetermined level by an external heat circulator, to a jacket of the (meth)acrylic acid waste liquid-receiving section 510 .
  • the (meth)acrylic acid waste liquid in a liquid-gas mixture state by the heat exchange is supplied to the (meth)acrylic acid waste liquid-receiving section 510 of the distillation column.
  • a liquid phase in the liquid-gas mixture is put to the (meth)acrylic acid waste liquid-receiving section 510 again, while a gas phase is distilled through the distillation section 520 , and a part thereof is discharged from the top portion of the distillation column.
  • the gas phase discharged from the top portion of the distillation column is condensed into a liquid phase in a condenser 590 , while a part thereof is refluxed to the top portion of the distillation column, and the rest is obtained as a final product, (meth)acrylic acid.
  • the destructive distillation of the (meth)acrylic acid waste liquid is continuously performed.
  • the destructive distillation system 500 is operated such that the maximum height of the (meth)acrylic acid waste liquid in the (meth)acrylic acid waste liquid-receiving section 510 corresponds to 85% or more of the height of the top end of the heat exchanger tube of the natural circulation type of reboiler 550 .
  • the height of the top end of the heat exchanger tube of the natural circulation type of reboiler 550 means a vertical distance from any reference point (for example, the ground) to the top end of the heat exchanger tube equipped inside the natural circulation type of reboiler 550 , in the natural circulation type of reboiler 550 connected to the distillation column.
  • the height of the top end of the heat exchanger tube means a vertical distance from the ground to the top end (outlet portion) of the heat exchanger tube.
  • the height of the top end of the heat exchanger tube means a distance from the ground to the heat exchanger tube located vertically farthest from the ground.
  • the maximum height of the (meth)acrylic acid waste liquid in the (meth)acrylic acid waste liquid-receiving section 510 means a vertical distance from any reference point to the liquid head of the (meth)acrylic acid waste liquid-receiving section 510 .
  • operating conditions of the above-described destructive distillation system 500 enables stable use of the natural circulation type of reboiler 550 which does not require an operating part in the destructive distillation process of recovering (meth)acrylic acid from the (meth)acrylic acid waste liquid.
  • the destructive distillation system 500 is operated such that the maximum height of the (meth)acrylic acid waste liquid in the (meth)acrylic acid waste liquid-receiving section 510 corresponds to 85% or more, 90% or more, 94% or more, 95% or more, 100% or more, 104% or more, 105% or more, 110% or more, 114% or more, 115% or more, 120% or more, 150% or more, 85% to 150%, 85% to 120%, 90% to 115%, or 94% to 114% of the height of the top end of the heat exchanger tube of the natural circulation type of reboiler 550 .
  • the destructive distillation system 500 should be operated such that the maximum height of the (meth)acrylic acid waste liquid in the (meth)acrylic acid waste liquid-receiving section 510 corresponds to 85% or more of the height of the top end of the heat exchanger tube of the natural circulation type of reboiler 550 , and as the ratio is higher, natural circulation may be more stably maintained.
  • the ratio of the height may be determined by considering a feed inlet height of the distillation column, a volume of the (meth)acrylic acid waste liquid-receiving section 510 in the distillation column, an installation height of the natural circulation type of reboiler 550 , a kind of the natural circulation type of reboiler 550 , etc.
  • Stable circulation of the (meth)acrylic acid waste liquid in the destructive distillation system 500 may be confirmed by temperature profiles in the distillation section 520 of the distillation column, flooding in the trays of the distillation column 520 , a temperature fluctuation width at each point inside the natural circulation type of reboiler 550 , etc.
  • the temperature fluctuation width inside the heat exchanger tube which is measured at points corresponding to 25%, 50%, 75%, and 100% in the longitudinal direction of the heat exchanger tube of the natural circulation type of reboiler 550 may be as narrow as 4.5° C. or less, 4° C. or less, 2° C. or less, or 1° C. or less, respectively.
  • the natural circulation type of reboiler 550 may be a vertical thermosiphon reboiler as in FIG. 2 , or a horizontal thermosiphon reboiler as in FIG. 3 .
  • the vertical thermosiphon reboiler may be more preferably used because it enables more stable natural circulation of high-viscosity (meth)acrylic acid waste liquid.
  • the distillation section 520 of the distillation column may be a multistage tray column with a perforated plate, and preferably, a sieve tray column or a dual-flow tray column.
  • the (meth)acrylic acid which is obtained as a final product through the above-described processes may be recycled to a high-boiling-point by-product separation column to be recovered as crude (meth)acrylic acid, or to be obtained as (meth)acrylic acid with high purity through an additional crystallization process.
  • a method of continuously recovering (meth)acrylic acid according to the present disclosure enables use of a natural circulation type of reboiler which does not require an operating part in a destructive distillation process of recovering (meth)acrylic acid from a (meth)acrylic acid waste liquid, and therefore, stable operation of the continuous process may be achieved while simplifying equipment configuration.
  • FIG. 1 shows an apparatus for preparing (meth)acrylic acid and a process diagram showing an overall flowchart
  • FIGS. 2 and 3 each show a destructive distillation system which is used for continuous recovery of (meth)acrylic acid from a (meth)acrylic acid waste liquid and a process diagram showing a flowchart.
  • HPAA High-purity (meth)acrylic acid
  • a temperature of an indirect heat exchange medium flowing into the outer space of the natural circulation type of reboiler 550 was 175° C., and a pressure at the top end of the distillation column was 50 torr.
  • a distillate discharged from the upper portion of the distillation section 520 was condensed into a liquid phase through a condenser 590 , and 50% by weight of the condensed liquid phase was refluxed into the upper portion of the distillation section 520 .
  • a reflux ratio was 1.0, and the rest thereof was discharged as a final product.
  • the destructive distillation system 500 was operated such that the maximum height of the (meth)acrylic acid waste liquid in the (meth)acrylic acid waste liquid-receiving section 510 was maintained at 114% of the height of the top end of the heat exchanger tube of the natural circulation type of reboiler 550 .
  • the (meth)acrylic acid waste liquid was continuously circulated by the natural circulation type of reboiler 550 , the temperature fluctuation width at each point inside the reboiler was 0.4° C. to 0.8° C., and a temperature profile of the distillation section was stably maintained throughout the operation time.
  • the (meth)acrylic acid waste liquid was continuously circulated by the natural circulation type of reboiler 550 , the temperature fluctuation width at each point inside the reboiler was 0.5° C. to 1.8° C., and a temperature profile of the distillation section was stably maintained throughout the operation time.
  • the (meth)acrylic acid waste liquid was continuously circulated by the natural circulation type of reboiler 550 , the temperature fluctuation width at each point inside the reboiler was 1° C. to 4.2° C., and a temperature profile of the distillation section was stably maintained throughout the operation time.
  • the (meth)acrylic acid waste liquid was discontinuously circulated while showing a pulse flow.
  • the temperature of the waste liquid in the (meth)acrylic acid waste liquid-receiving section 510 was decreased to 130° C. or lower, and an inner temperature of the heat exchanger tube, which was measured at the point corresponding to 25% in the longitudinal direction of the heat exchanger tube of the natural circulation type of reboiler 550 , showed a fluctuation from 130.7° C. to 161.9° C. and stable operation of the destructive distillation process was not achieved. Further, a temperature profile of the distillation section 520 showed unstable patterns, and the system was operated with some empty trays.

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Abstract

A method of continuously recovering (meth)acrylic acid is provided. The method of continuously recovering (meth)acrylic acid according to the present disclosure enables use of a natural circulation type of reboiler which does not require an operating part in a destructive distillation process of recovering (meth)acrylic acid from a (meth)acrylic acid waste liquid, and therefore, stable operation of the continuous process may be achieved while simplifying equipment configuration.

Description

CROSS-REFERENCE TO RELATED APPLICATION
This application is a National Stage Application of International Application No. PCT/KR2016/011646, filed Oct. 17, 2016, and claims the benefit of Korean Patent Application No. 10-2015-0184161, filed on Dec. 22, 2015, the contents of which are incorporated herein by reference in their entirety for all purposes as if fully set forth below.
TECHNICAL FIELD
The present disclosure relates to a method of continuously recovering (meth)acrylic acid, and more particularly, to a method of continuously recovering (meth)acrylic acid from a (meth)acrylic acid waste liquid including (meth)acrylic acid, (meth)acrylic acid dimers, and high-boiling-point by-products.
BACKGROUND OF ART
(Meth)acrylic acid which is a main raw material of a superabsorbent polymer (SAP) is generally obtained by gas-phase oxidation reaction of propylene, etc.
For example, a raw material compound, such as propane, propylene, (meth)acrolein, etc., is subjected to gas-phase oxidation reaction in the presence of a catalyst to obtain a (meth)acrylic acid-containing mixed gas, which is then condensed or absorbed into an absorption solvent and collected as a (meth)acrylic acid-containing solution. From this (meth)acrylic acid-containing solution, low-boiling-point components such as the absorption solvent, (meth)acrylic acid dimers, (meth)acrylic acid oligomers, and high-boiling-point by-products such as maleic acid are separated by a series of purification processes to obtain crude (meth)acrylic acid.
A waste liquid obtained as a waste material in the process of separating the high-boiling-point by-products includes part of unrecovered (meth)acrylic acid, (meth)acrylic acid dimers, and high-boiling-point by-products such as maleic acid which are generated during the purification process.
In particular, it is known that a large amount of the (meth)acrylic acid dimers included in the waste liquid (hereinafter referred to as ‘(meth)acrylic acid waste liquid’) may be recovered as (meth)acrylic acid through a high-temperature or catalytic reaction.
Therefore, disposal of the (meth)acrylic acid waste liquid leads to a loss of (meth) acrylic acid, which is economically disadvantageous. For this reason, a variety of methods of stably recovering (meth)acrylic acid from the (meth)acrylic acid waste liquid have been suggested.
However, there are limitations in that most of the methods require complicated equipment and high energy consumption, and stability of the process operation is still low.
PRIOR ART DOCUMENTS Patent Document
(Patent Document 1) U.S. Pat. No. 6,252,110 B1 (2001 Jun. 26)
DETAILED DESCRIPTION OF THE INVENTION Technical Problem
The present disclosure provides a method of continuously recovering (meth)acrylic acid which enables stable operation of a continuous process while simplifying equipment configuration of a destructive distillation process of recovering (meth) acrylic acid from a (meth) acrylic acid waste liquid.
Technical Solution
According to the present disclosure, a method of continuously recovering (meth)acrylic acid from a (meth)acrylic acid waste liquid including (meth)acrylic acid, (meth)acrylic acid dimers, and high-boiling-point by-products is provided,
wherein the recovering of (meth)acrylic acid is performed in a destructive distillation system 500 including a distillation column including a (meth)acrylic acid waste liquid-receiving section 510 and a distillation section 520 at the top portion thereof, and a natural circulation type of reboiler 550 which is connected to the distillation column and heats a liquid discharged from the lower portion of the distillation column by passing the liquid through a plurality of heat exchanger tubes to supply the liquid to the (meth)acrylic acid waste liquid-receiving section 510 of the distillation column, and
the destructive distillation system 500 is operated such that the maximum height of the (meth)acrylic acid waste liquid in the (meth)acrylic acid waste liquid-receiving section 510 corresponds to 85% or more of the height of the top end of the heat exchanger tube of the natural circulation type of reboiler 550.
Hereinafter, a method of continuously recovering (meth)acrylic acid according to embodiments of the present disclosure will be described in more detail.
The terminology used in this description is just for explaining exemplary embodiments, and it is not intended to restrict the present disclosure.
The singular expressions used herein may include the plural expressions unless it is differently expressed contextually. Further, the term “include”, when used in this specification, specifies the presence of stated features, regions, integers, steps, operations, elements, or components, but does not preclude the addition of other features, regions, integers, steps, operations, elements, or components.
As used herein, the term ‘(meth)acrylic acid’ means acrylic acid and/or methacrylic acid.
As used herein, the term ‘(meth)acrylic acid-containing mixed gas’ refers to a mixed gas which may be produced during synthesis of (meth)acrylic acid by gas-phase oxidation reaction. As a non-limiting example, the (meth)acrylic acid-containing mixed gas may be obtained by gas-phase oxidation of one or more compounds (‘raw material compounds’) selected from the group consisting of propane, propylene, butane, isobutylene, and (meth)acrolein in the presence of a catalyst.
The (meth)acrylic acid-containing mixed gas may include (meth)acrylic acid, non-reacted raw material compounds, (meth)acrolein, an inert gas, carbon monoxide, carbon dioxide, water vapor, and various organic by-products (acetic acid, low-boiling-point by-products (light ends), high-boiling-point by-products (heavies), etc.). Here, the ‘low-boiling-point by-products’ (light ends) or ‘high-boiling-point by-products’ (heavies) are kinds of by-products that may be generated in the process of preparing and recovering desired (meth)acrylic acid, and generally refer to compounds having a smaller or larger molecular weight than (meth)acrylic acid.
Meanwhile, in a distillation system using a natural circulation type of reboiler, natural circulation may be caused by a density difference due to a temperature gradient between a material (a liquid to be distilled) injected into the reboiler and a material (a liquid-gas mixture produced by heat exchange) discharged from the reboiler.
When this natural circulation type of reboiler is stably operated, an operating part such as a pump is not required, and thus there are advantages that equipment configuration may be simplified and energy consumption may be reduced. In general, the natural circulation type of reboiler is used for a liquid having viscosity of 0.5 cP or less under operating conditions and a low fouling tendency at the inner wall of the heat exchanger tube of the reboiler in the case where a pressure in the reaction system is high.
However, the (meth)acrylic acid waste liquid obtained during the process of preparing (meth)acrylic acid has high viscosity of 20 cP to 60 cP at 100° C. to 150° C., and shows a high fouling tendency at the inner wall of the heat exchanger tube of the reboiler when it is exposed to a high temperature.
Further, when the (meth)acrylic acid waste liquid having high viscosity is applied to the natural circulation type of reboiler, continuous liquid circulation does not occur but a pulse flow occurs. As a result, the temperature inside the reboiler may fluctuate severely, flooding may occur in trays of the distillation column connected to the reboiler, or the system may be operated with some empty trays.
It is known that use of the natural circulation type of reboiler in the distillation of high-viscosity (meth)acrylic acid waste liquid is restricted or practically impossible. Usually, kettle reboilers, fired reboilers, forced circulation reboilers, etc. are used.
However, according to the experimental results of the present inventors, it is possible to use the natural circulation type of reboiler when the system is operated such that the liquid head of the (meth)acrylic acid waste liquid-receiving section corresponds to 85% or more of the height of the top end of the heat exchanger tube equipped inside the natural circulation type of reboiler. Accordingly, equipment configuration for obtaining (meth)acrylic acid from the (meth)acrylic acid waste liquid may be simplified, and stable operation of a continuous process is also possible.
According to an embodiment of the present disclosure, in a method of recovering (meth)acrylic acid from a (meth)acrylic acid waste liquid including (meth)acrylic acid, (meth)acrylic acid dimers, and high-boiling-point by-products,
the recovering of (meth)acrylic acid is performed in a destructive distillation system 500 including a distillation column including a (meth)acrylic acid waste liquid-receiving section 510 and a distillation section 520 at the top portion thereof, and a natural circulation type of reboiler 550 which is connected to the distillation column and heats the liquid discharged from the bottom of the distillation column by passing the liquid through a plurality of heat exchanger tubes to supply the liquid to the (meth)acrylic acid waste liquid-receiving section 510 of the distillation column, and
the destructive distillation system 500 is operated such that the maximum height of the (meth)acrylic acid waste liquid in the (meth)acrylic acid waste liquid-receiving section 510 corresponds to 85% or more of the height of the top end of the heat exchanger tube of the natural circulation type of reboiler 550.
The present disclosure relates to the method of continuously recovering (meth)acrylic acid from a (meth)acrylic acid waste liquid including (meth)acrylic acid, (meth)acrylic acid dimers, and high-boiling-point by-products by destructive distillation.
As a non-limiting example, FIG. 1 shows an apparatus for preparing (meth)acrylic acid and a process diagram showing an overall flowchart. The (meth)acrylic acid waste liquid is a liquid discharged from the lower part of a high-boiling-point by-product separation column 400.
In other words, the (meth)acrylic acid waste liquid is obtained as waste in the process of separating the high-boiling-point by-products during a series of purification processes of the (meth)acrylic acid-containing solution, and includes part of unrecovered (meth)acrylic acid, and (meth)acrylic acid dimers and high-boiling-point by-products such as maleic acid which are generated during the purification process.
Here, the (meth)acrylic acid-containing solution refers to a solution collected by condensing a (meth)acrylic acid-containing mixed gas or absorbing the (meth)acrylic acid-containing mixed gas into an absorption solvent, in which the (meth)acrylic acid-containing mixed gas is obtained by subjecting a raw material compound such as propane, propylene, (meth)acrolein, etc. to gas-phase oxidation reaction in the presence of a catalyst.
In particular, the (meth)acrylic acid waste liquid includes a large amount of (meth)acrylic acid dimers which are formed during the purification process, and the (meth)acrylic acid dimers may be recovered as (meth)acrylic acid by decomposition through a high-temperature or catalytic reaction.
FIGS. 2 and 3 show a destructive distillation system which is used for continuous recovery of (meth)acrylic acid from the (meth)acrylic acid waste liquid and a process diagram showing a flowchart according to embodiments of the present disclosure, respectively.
According to embodiments of the present disclosure, the recovery of (meth)acrylic acid may be performed in the destructive distillation system 500 including a distillation column including a (meth)acrylic acid waste liquid-receiving section 510 and a distillation section 520 at the top portion thereof, and a natural circulation type of reboiler 550 which is connected to the distillation column and heats the liquid discharged from the lower portion of the distillation column by passing the liquid through a plurality of heat exchanger tubes to supply the liquid to the (meth)acrylic acid waste liquid-receiving section 510 of the distillation column.
Particularly, in the destructive distillation system 500, the (meth)acrylic acid waste liquid as a feed is supplied to the distillation column and received in the (meth)acrylic acid waste liquid-receiving section 510 at an arbitrary liquid level.
The (meth)acrylic acid waste liquid-receiving section 510 is maintained at a temperature level at which the thermal decomposition of the (meth)acrylic acid waste liquid may occur. For example, the destructive distillation system 500 may be operated such that the temperature of the (meth)acrylic acid waste liquid-receiving section 510 is maintained at 100° C. to 200° C., and preferably 130° C. to 180° C. This temperature control may be performed by supplying a heating medium, which is heated to a predetermined level by an external heat circulator, to a jacket of the (meth)acrylic acid waste liquid-receiving section 510.
While the (meth)acrylic acid waste liquid supplied from the lower portion of the distillation column to the natural circulation type of reboiler 550 passes through a plurality of heat exchanger tubes which are equipped inside the natural circulation type of reboiler 550, heat exchange occurs.
The (meth)acrylic acid waste liquid in a liquid-gas mixture state by the heat exchange is supplied to the (meth)acrylic acid waste liquid-receiving section 510 of the distillation column.
A liquid phase in the liquid-gas mixture is put to the (meth)acrylic acid waste liquid-receiving section 510 again, while a gas phase is distilled through the distillation section 520, and a part thereof is discharged from the top portion of the distillation column. The gas phase discharged from the top portion of the distillation column is condensed into a liquid phase in a condenser 590, while a part thereof is refluxed to the top portion of the distillation column, and the rest is obtained as a final product, (meth)acrylic acid.
The destructive distillation of the (meth)acrylic acid waste liquid is continuously performed.
In particular, according to embodiments of the present disclosure, the destructive distillation system 500 is operated such that the maximum height of the (meth)acrylic acid waste liquid in the (meth)acrylic acid waste liquid-receiving section 510 corresponds to 85% or more of the height of the top end of the heat exchanger tube of the natural circulation type of reboiler 550.
Here, the height of the top end of the heat exchanger tube of the natural circulation type of reboiler 550 means a vertical distance from any reference point (for example, the ground) to the top end of the heat exchanger tube equipped inside the natural circulation type of reboiler 550, in the natural circulation type of reboiler 550 connected to the distillation column.
For example, in the case of the natural circulation type of reboiler 550 equipped with the heat exchanger tube in a vertical direction with respect to the ground as in the destructive distillation system 500 of FIG. 2, the height of the top end of the heat exchanger tube means a vertical distance from the ground to the top end (outlet portion) of the heat exchanger tube.
Further, in the case of the natural circulation type of reboiler 550 equipped with the heat exchanger tube in a horizontal direction with respect to the ground as in the destructive distillation system 500 of FIG. 3, the height of the top end of the heat exchanger tube means a distance from the ground to the heat exchanger tube located vertically farthest from the ground.
The maximum height of the (meth)acrylic acid waste liquid in the (meth)acrylic acid waste liquid-receiving section 510 means a vertical distance from any reference point to the liquid head of the (meth)acrylic acid waste liquid-receiving section 510.
According to the present disclosure, operating conditions of the above-described destructive distillation system 500 enables stable use of the natural circulation type of reboiler 550 which does not require an operating part in the destructive distillation process of recovering (meth)acrylic acid from the (meth)acrylic acid waste liquid.
Preferably, the destructive distillation system 500 is operated such that the maximum height of the (meth)acrylic acid waste liquid in the (meth)acrylic acid waste liquid-receiving section 510 corresponds to 85% or more, 90% or more, 94% or more, 95% or more, 100% or more, 104% or more, 105% or more, 110% or more, 114% or more, 115% or more, 120% or more, 150% or more, 85% to 150%, 85% to 120%, 90% to 115%, or 94% to 114% of the height of the top end of the heat exchanger tube of the natural circulation type of reboiler 550.
In other words, to enable the use of the natural circulation type of reboiler (550) in the destructive distillation process of recovering (meth)acrylic acid from the (meth)acrylic acid waste liquid, the destructive distillation system 500 should be operated such that the maximum height of the (meth)acrylic acid waste liquid in the (meth)acrylic acid waste liquid-receiving section 510 corresponds to 85% or more of the height of the top end of the heat exchanger tube of the natural circulation type of reboiler 550, and as the ratio is higher, natural circulation may be more stably maintained.
The ratio of the height may be determined by considering a feed inlet height of the distillation column, a volume of the (meth)acrylic acid waste liquid-receiving section 510 in the distillation column, an installation height of the natural circulation type of reboiler 550, a kind of the natural circulation type of reboiler 550, etc.
According to embodiments of the present disclosure, when the destructive distillation system 500 is operated under the above-described conditions, natural and stable circulation of the (meth)acrylic acid waste liquid by the natural circulation type of reboiler is possible.
Stable circulation of the (meth)acrylic acid waste liquid in the destructive distillation system 500 may be confirmed by temperature profiles in the distillation section 520 of the distillation column, flooding in the trays of the distillation column 520, a temperature fluctuation width at each point inside the natural circulation type of reboiler 550, etc.
For example, the temperature fluctuation width inside the heat exchanger tube which is measured at points corresponding to 25%, 50%, 75%, and 100% in the longitudinal direction of the heat exchanger tube of the natural circulation type of reboiler 550 may be as narrow as 4.5° C. or less, 4° C. or less, 2° C. or less, or 1° C. or less, respectively.
In contrast, when a pulse flow occurs due to unstable circulation in the reboiler, the temperature fluctuation width becomes large at each point inside the reboiler, temperature profiles in the distillation section 520 are unstable, or the system is operated with some empty trays, i.e., continuous operation is impossible.
Meanwhile, according to embodiments of the present invention, as the natural circulation type of reboiler 550, those having any configuration known in the art to which the present invention pertains may be used without particular limitation.
Preferably, the natural circulation type of reboiler 550 may be a vertical thermosiphon reboiler as in FIG. 2, or a horizontal thermosiphon reboiler as in FIG. 3.
The vertical thermosiphon reboiler may be more preferably used because it enables more stable natural circulation of high-viscosity (meth)acrylic acid waste liquid.
The distillation section 520 of the distillation column may be a multistage tray column with a perforated plate, and preferably, a sieve tray column or a dual-flow tray column.
The (meth)acrylic acid which is obtained as a final product through the above-described processes may be recycled to a high-boiling-point by-product separation column to be recovered as crude (meth)acrylic acid, or to be obtained as (meth)acrylic acid with high purity through an additional crystallization process.
Advantageous Effects
A method of continuously recovering (meth)acrylic acid according to the present disclosure enables use of a natural circulation type of reboiler which does not require an operating part in a destructive distillation process of recovering (meth)acrylic acid from a (meth)acrylic acid waste liquid, and therefore, stable operation of the continuous process may be achieved while simplifying equipment configuration.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows an apparatus for preparing (meth)acrylic acid and a process diagram showing an overall flowchart; and
FIGS. 2 and 3 each show a destructive distillation system which is used for continuous recovery of (meth)acrylic acid from a (meth)acrylic acid waste liquid and a process diagram showing a flowchart.
 REFERENCE NUMERALS
500: Destructive distillation system
510: (Meth)acrylic acid waste liquid-receiving section
520: Distillation section
550: Natural circulation type of reboiler
590: Condenser
1: (Meth)acrylic acid-containing mixed gas
100: (Meth)acrylic acid absorption tower
102: (Meth)acrylic acid aqueous solution transfer line
150: Acetic acid absorption tower
200: (Meth)acrylic acid extraction column
203: Extract transfer line
253: Filtrate transfer line
300: Distillation column
350: Phase separation tank
400: High boiling point by-product separation column
CAA: Crude (meth)acrylic acid
HPAA: High-purity (meth)acrylic acid
DETAILED DESCRIPTION OF THE EMBODIMENTS
Hereinafter, preferred examples are provided for better understanding. However, these examples are for illustrative purposes only, and the present invention is not intended to be limited by these examples.
Example 1
A destructive distillation system 500 equipped with a distillation column consisting of a (meth)acrylic acid waste liquid-receiving section 510 having an inner diameter of 7 cm and a height of 100 cm and a distillation section 520 including a total of 9 dual-flow trays having an inner diameter of 3 cm, a tray spacing of 10 cm, and a tray opening ratio of 14%, and a natural circulation type of reboiler 550 having an inner diameter of 1 inch and a height of 100 cm was prepared as in FIG. 2.
A temperature of an indirect heat exchange medium flowing into the outer space of the natural circulation type of reboiler 550 was 175° C., and a pressure at the top end of the distillation column was 50 torr.
A distillate discharged from the upper portion of the distillation section 520 was condensed into a liquid phase through a condenser 590, and 50% by weight of the condensed liquid phase was refluxed into the upper portion of the distillation section 520. As a result, a reflux ratio was 1.0, and the rest thereof was discharged as a final product.
The destructive distillation system 500 was operated such that the maximum height of the (meth)acrylic acid waste liquid in the (meth)acrylic acid waste liquid-receiving section 510 was maintained at 114% of the height of the top end of the heat exchanger tube of the natural circulation type of reboiler 550.
Inner temperatures of the heat exchanger tube were measured at points corresponding to 25%, 50%, 75%, and 100% in the longitudinal direction of the heat exchanger tube of the natural circulation type of reboiler 550, and are shown in the following Table 1.
As a result, the (meth)acrylic acid waste liquid was continuously circulated by the natural circulation type of reboiler 550, the temperature fluctuation width at each point inside the reboiler was 0.4° C. to 0.8° C., and a temperature profile of the distillation section was stably maintained throughout the operation time.
Example 2
Operation was performed in the same manner as in Example 1, except that the destructive distillation system 500 was operated such that the maximum height of the (meth)acrylic acid waste liquid in the (meth)acrylic acid waste liquid-receiving section 510 was maintained at 104% of the height of the top end of the heat exchanger tube of the natural circulation type of reboiler 550.
Inner temperatures of the heat exchanger tube were measured at points corresponding to 25%, 50%, 75%, and 100% in the longitudinal direction of the heat exchanger tube of the natural circulation type of reboiler 550, and are shown in the following Table 1.
As a result, the (meth)acrylic acid waste liquid was continuously circulated by the natural circulation type of reboiler 550, the temperature fluctuation width at each point inside the reboiler was 0.5° C. to 1.8° C., and a temperature profile of the distillation section was stably maintained throughout the operation time.
Example 3
Operation was performed in the same manner as in Example 1, except that the destructive distillation system 500 was operated such that the maximum height of the (meth)acrylic acid waste liquid in the (meth)acrylic acid waste liquid-receiving section 510 was maintained at 94% of the height of the top end of the heat exchanger tube of the natural circulation type of reboiler 550.
Inner temperatures of the heat exchanger tube were measured at points corresponding to 25%, 50%, 75%, and 100% in the longitudinal direction of the heat exchanger tube of the natural circulation type of reboiler 550, and are shown in the following Table 1.
As a result, the (meth)acrylic acid waste liquid was continuously circulated by the natural circulation type of reboiler 550, the temperature fluctuation width at each point inside the reboiler was 1° C. to 4.2° C., and a temperature profile of the distillation section was stably maintained throughout the operation time.
Comparative Example 1
Operation was performed in the same manner as in Example 1, except that the destructive distillation system 500 was operated such that the maximum height of the (meth)acrylic acid waste liquid in the (meth)acrylic acid waste liquid-receiving section 510 was maintained at 84% of the height of the top end of the heat exchanger tube of the natural circulation type of reboiler 550.
Inner temperatures of the heat exchanger tube were measured at the point corresponding to 25%, 50%, 75%, and 100% in the longitudinal direction of the heat exchanger tube of the natural circulation type of reboiler 550, and are shown in the following Table 1.
As a result, the (meth)acrylic acid waste liquid was discontinuously circulated while showing a pulse flow. As a result, the temperature of the waste liquid in the (meth)acrylic acid waste liquid-receiving section 510 was decreased to 130° C. or lower, and an inner temperature of the heat exchanger tube, which was measured at the point corresponding to 25% in the longitudinal direction of the heat exchanger tube of the natural circulation type of reboiler 550, showed a fluctuation from 130.7° C. to 161.9° C. and stable operation of the destructive distillation process was not achieved. Further, a temperature profile of the distillation section 520 showed unstable patterns, and the system was operated with some empty trays.
TABLE 1
Temperature at each
point of tube inside reboiler
100%
point 75% point 50% point 25% point
Example 1 Maximum 137.6 143.3 156.2 141.4
Average 137.4 143.0 155.8 141.0
Minimum 137.2 142.6 155.4 140.6
Fluctuation 0.4 0.7 0.8 0.8
width
Example 2 Maximum 141.2 147.0 155.9 145.8
Average 141.0 146.6 155.5 144.9
Minimum 140.7 146.1 155.0 144.0
Fluctuation 0.5 0.9 0.9 1.8
width
Example 3 Maximum 146.1 150.5 157.9 148.5
Average 145.6 149.9 157.3 146.4
Minimum 145.1 149.2 156.7 144.3
Fluctuation 1 1.3 1.2 4.2
width
Comparative Maximum 153.5 158.0 164.3 161.9
Example 1 Average 151.6 155.8 159.1 146.3
Minimum 149.6 153.5 153.8 130.7
Fluctuation 3.9 4.5 10.5 31.2
width

Claims (3)

The invention claimed is:
1. A method of continuously recovering (meth)acrylic acid from a (meth)acrylic acid waste liquid including (meth)acrylic acid, (meth)acrylic acid dimers, and high-boiling-point by-products,
wherein the recovering of (meth)acrylic acid is performed in a destructive distillation system including a distillation column including a (meth)acrylic acid waste liquid-receiving section and a distillation section at the top portion thereof, and a natural circulation type of reboiler which is connected to the distillation column and heats the liquid discharged from the lower portion of the distillation column by passing the liquid through a plurality of heat exchanger tubes to supply the liquid to the (meth)acrylic acid waste liquid-receiving section of the distillation column, and
the destructive distillation system is operated such that the maximum height of the (meth)acrylic acid waste liquid in the (meth)acrylic acid waste liquid-receiving section corresponds to 85% to 100% or more of the height of the top end of the heat exchanger tube of the natural circulation type of reboiler.
2. The method of continuously recovering (meth)acrylic acid of claim 1, wherein a temperature fluctuation width inside the heat exchanger tube which is measured at points corresponding to 25%, 50%, 75%, and 100% in the longitudinal direction of the heat exchanger tube of the natural circulation type of reboiler is 4.5° C. or less, respectively.
3. The method of continuously recovering (meth)acrylic acid of claim 1, wherein the natural circulation type of reboiler is a vertical thermosiphon reboiler or a horizontal thermosiphon reboiler.
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Citations (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4317926A (en) 1978-01-19 1982-03-02 Nippon Shokubai Kagaku Kogyo Co., Ltd. Process for preparing and recovering acrylic acid
US5734075A (en) 1994-12-12 1998-03-31 Elf Atochem S.A. Process for recovery of the light noble products present in the distillation residues from the processes for the manufacture of acrylic acid and of its esters
JPH1112222A (en) 1997-06-25 1999-01-19 Nippon Shokubai Co Ltd Recovery of acrylic acid
JP2861983B2 (en) 1997-04-07 1999-02-24 東亞合成株式会社 Decomposition method of Michael adduct of acrylic acid ester
US5897749A (en) 1995-10-23 1999-04-27 Basf Aktiengesellschaft Continuous distillative separation of liquid mixtures which contain (meth) acrylic acid as the main component
JP2000239229A (en) 1999-02-18 2000-09-05 Nippon Shokubai Co Ltd Distillation of readily polymerizable compound or liquid containing readily polymerizable compound
JP2000256258A (en) 1999-03-09 2000-09-19 Nippon Shokubai Co Ltd Production of (meth)acrylic acid and/or its ester
JP2001190901A (en) 1999-10-29 2001-07-17 Nippon Shokubai Co Ltd Distillation equipment and distillation method
JP2003171342A (en) 2001-12-05 2003-06-20 Mitsubishi Chemicals Corp Method for decomposing byproduct in producing (meth) acrylic acid compound
JP2003192641A (en) 2001-12-25 2003-07-09 Mitsubishi Rayon Co Ltd Reboiler facility and method for heating solution containing easily polymerizable substance
US6632329B1 (en) 1999-10-29 2003-10-14 Nippon Shokubai Co., Ltd. Distillation apparatus and distilling method
US6642414B2 (en) 2000-02-03 2003-11-04 Nippon Shokubai Co., Ltd. Method for production of (meth) acrylic acid
JP2005177633A (en) 2003-12-19 2005-07-07 Mitsubishi Rayon Co Ltd Distillation column and distillation device equipped with the same
US7014736B2 (en) 2003-03-18 2006-03-21 Nippon Shokubai Co., Ltd. Apparatus and process for purification of acrylic acid family
KR100714631B1 (en) 2004-04-29 2007-05-07 주식회사 엘지화학 Method for recovering acrylic acid
JP3918528B2 (en) 2001-11-27 2007-05-23 三菱化学株式会社 (Meth) acrylic acid purification method
US7342130B2 (en) 2005-12-06 2008-03-11 Nippon Shokubai Co., Ltd. Method for producing acrylic acid
US7388109B2 (en) 2004-07-01 2008-06-17 Basf Aktiengesellschaft Preparation of acrolein or acrylic acid or a mixture thereof from propane
US20080183014A1 (en) 2007-01-26 2008-07-31 Basf Se Process for preparing acrylic acid
US20090253934A1 (en) 2006-09-15 2009-10-08 Fungau Ho Process for Producing Acrylic Acid
JP2009242286A (en) 2008-03-31 2009-10-22 Mitsubishi Chemicals Corp Method for producing acrylic acid
US20100217030A1 (en) 2007-11-23 2010-08-26 Evonik Roehm Gmbh Method and plant for purifying unsaturated compounds
US20100286443A1 (en) 2006-12-28 2010-11-11 Nippon Shokubai Co. Ltd Method for producing (meth) acrylic acid
JP5104275B2 (en) 2007-12-12 2012-12-19 三菱化学株式会社 Method for collecting polymerization inhibitor
CN102971057A (en) 2010-05-13 2013-03-13 阿文戈亚太阳能新技术有限公司 Plant for recovering degraded heat transfer oil from a solar thermal facility and associated recovery method
JP2014070069A (en) 2012-10-02 2014-04-21 Sumitomo Chemical Co Ltd Apparatus and method for separating/recovering (meth)acrylic acid
JP5715318B2 (en) 2005-12-06 2015-05-07 株式会社日本触媒 Acrylic acid production method
JP2015174851A (en) 2014-03-17 2015-10-05 三菱化学株式会社 Method for producing (meth)acrylic acid

Patent Citations (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4317926A (en) 1978-01-19 1982-03-02 Nippon Shokubai Kagaku Kogyo Co., Ltd. Process for preparing and recovering acrylic acid
US5734075A (en) 1994-12-12 1998-03-31 Elf Atochem S.A. Process for recovery of the light noble products present in the distillation residues from the processes for the manufacture of acrylic acid and of its esters
US5897749A (en) 1995-10-23 1999-04-27 Basf Aktiengesellschaft Continuous distillative separation of liquid mixtures which contain (meth) acrylic acid as the main component
KR100464841B1 (en) 1995-10-23 2005-04-06 바스프 악티엔게젤샤프트 (Meth) acrylic acid as a main component is continuously distilled and separated
JP2861983B2 (en) 1997-04-07 1999-02-24 東亞合成株式会社 Decomposition method of Michael adduct of acrylic acid ester
JPH1112222A (en) 1997-06-25 1999-01-19 Nippon Shokubai Co Ltd Recovery of acrylic acid
US6252110B1 (en) * 1997-06-25 2001-06-26 Nippon Shokubai Co Ltd Methods for recovering acrylic acid
US6666956B1 (en) * 1999-02-18 2003-12-23 Nippon Shokubai Co., Ltd. Method for distilling polymerizable compound or liquid containing polymerizable compound
JP2000239229A (en) 1999-02-18 2000-09-05 Nippon Shokubai Co Ltd Distillation of readily polymerizable compound or liquid containing readily polymerizable compound
JP2000256258A (en) 1999-03-09 2000-09-19 Nippon Shokubai Co Ltd Production of (meth)acrylic acid and/or its ester
US6348135B1 (en) 1999-03-09 2002-02-19 Nippon Shokubai Co., Ltd. Process for the purification of (meth) acrylic acid and/or its ester
JP2001190901A (en) 1999-10-29 2001-07-17 Nippon Shokubai Co Ltd Distillation equipment and distillation method
US6632329B1 (en) 1999-10-29 2003-10-14 Nippon Shokubai Co., Ltd. Distillation apparatus and distilling method
US6642414B2 (en) 2000-02-03 2003-11-04 Nippon Shokubai Co., Ltd. Method for production of (meth) acrylic acid
JP3918528B2 (en) 2001-11-27 2007-05-23 三菱化学株式会社 (Meth) acrylic acid purification method
JP2003171342A (en) 2001-12-05 2003-06-20 Mitsubishi Chemicals Corp Method for decomposing byproduct in producing (meth) acrylic acid compound
JP2003192641A (en) 2001-12-25 2003-07-09 Mitsubishi Rayon Co Ltd Reboiler facility and method for heating solution containing easily polymerizable substance
US7014736B2 (en) 2003-03-18 2006-03-21 Nippon Shokubai Co., Ltd. Apparatus and process for purification of acrylic acid family
JP2005177633A (en) 2003-12-19 2005-07-07 Mitsubishi Rayon Co Ltd Distillation column and distillation device equipped with the same
KR100714631B1 (en) 2004-04-29 2007-05-07 주식회사 엘지화학 Method for recovering acrylic acid
US8308913B2 (en) 2004-04-29 2012-11-13 Lg Chem, Ltd. Apparatus for recovering acrylic acid
US7388109B2 (en) 2004-07-01 2008-06-17 Basf Aktiengesellschaft Preparation of acrolein or acrylic acid or a mixture thereof from propane
JP5156375B2 (en) 2004-07-01 2013-03-06 ビーエーエスエフ ソシエタス・ヨーロピア Production of acrolein or acrylic acid or mixtures thereof from propane
JP5715318B2 (en) 2005-12-06 2015-05-07 株式会社日本触媒 Acrylic acid production method
US7342130B2 (en) 2005-12-06 2008-03-11 Nippon Shokubai Co., Ltd. Method for producing acrylic acid
KR100932467B1 (en) 2005-12-06 2009-12-17 니폰 쇼쿠바이 컴파니 리미티드 Method of producing acrylic acid
US20090253934A1 (en) 2006-09-15 2009-10-08 Fungau Ho Process for Producing Acrylic Acid
US20100286443A1 (en) 2006-12-28 2010-11-11 Nippon Shokubai Co. Ltd Method for producing (meth) acrylic acid
US20080183014A1 (en) 2007-01-26 2008-07-31 Basf Se Process for preparing acrylic acid
US20100217030A1 (en) 2007-11-23 2010-08-26 Evonik Roehm Gmbh Method and plant for purifying unsaturated compounds
JP2011504475A (en) 2007-11-23 2011-02-10 エボニック レーム ゲゼルシャフト ミット ベシュレンクテル ハフツング Unsaturated compound purification method and production apparatus
JP5104275B2 (en) 2007-12-12 2012-12-19 三菱化学株式会社 Method for collecting polymerization inhibitor
JP2009242286A (en) 2008-03-31 2009-10-22 Mitsubishi Chemicals Corp Method for producing acrylic acid
CN102971057A (en) 2010-05-13 2013-03-13 阿文戈亚太阳能新技术有限公司 Plant for recovering degraded heat transfer oil from a solar thermal facility and associated recovery method
US9211484B2 (en) 2010-05-13 2015-12-15 Abengoa Solar New Technologies, S.A. Plant for recovering degraded heat transfer oil from a solar thermal facility and method for said recovery
JP2014070069A (en) 2012-10-02 2014-04-21 Sumitomo Chemical Co Ltd Apparatus and method for separating/recovering (meth)acrylic acid
JP2015174851A (en) 2014-03-17 2015-10-05 三菱化学株式会社 Method for producing (meth)acrylic acid

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Arneth, et al.: "Characteristics of thermosiphon reboilers", XP004235249, International Journal of Thermal Science, Elsevier, vol. 40, No. 4, Apr. 1, 2001, pp. 385-391.
ARNETH, S. STICHLMAIR, J.: "Characteristics of thermosiphon reboilers", INTERNATIONAL JOURNAL OF THERMAL SCIENCES., EDITIONS ELSEVIER, PARIS., FR, vol. 40, no. 4, 1 April 2001 (2001-04-01), FR, pages 385 - 391, XP004235249, ISSN: 1290-0729, DOI: 10.1016/S1290-0729(01)01231-5

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